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Synthesis, Characterization Of New Schiff Base And Some

Metal Complexes Derived From Glyoxylic Acid And
O-Phenylenediamine
J. Sh. Sultan
Department of Chemistry,
University of Baghdad
Email: ja.sultan@yahoo.com.

College

of

Education,

Ibn-Al-Haitham,

Received in : 27 May 2012 Accepted in : 7 August 2012

Abstract
The new Schiff base, namely (2-Amino-phenylimino)-acetic acid (L) was prepared
from condensation of glyoxylic acid with o-phenylene diamine. The structure (L) was
characterized by, IR, 1H, 13C-NMR and CHN analysis. Metal complexes of the ligand (L)
were synthesized and their structures were characterized by Atomic absorption, IR and UVVisible spectra, molar conductivity, magnetic moment and molar ratio determination (Co+2,
Cd+2) complexes. All complexes showed octahedral geometries.
Key words: Synthesis, Characterization, Schiff base, glyoxylic acid, O-phenylenediamine
and metal ions

Introduction
Glyoxilic acid and its derivatives play important roles in natural processes,
participating in glyoxylate cycle which functions in plants and in some microorganism[1-4].
The presence of aldehyde in the glyoxilic acid allows numerous a cyclic derivatives
containing C=N bond- azomethines and hydrazones[5-8].
The aim of this work is to synthesize and study the coordination behaviour of the new
ligand (2-Amino-phenylimino)-acetic acid (L) and its complexes with Co+2, Ni+2, Cu+2 , Cd+2,
Hg+2 and Pb+2.

Experimental
All chemicals were purchased from BDH, and used without further purifications.

Instrumentation
1. FTIR spectra were recorded in KBr on Shimadzu- 8300 Spectrophotometer in the range of
(4000-400 cm1).
2. The electronic spectra in H2O were recorded using the UV-Visible spectrophotometer type
(spectra 190-900 nm) CECIL, England, with quartz cell of (1 cm) path length.
3. The melting point was recorded on "Gallen kamp Melting point Apparatus".
4. The Conductance Measurements were recorded on W. T. W. conductivity Meter.
5. Metal analysis. The metal contents of the complexes were determined by atomic absorption
(A. A.) technique. Using a shimadzu PR-5. ORAPHIC PRINTER atomic obsorption
spectrophotometer.
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6. Balance Magnetic Susceptibility model MSB-MLI Al-Nahrain University

7. The characterize of new ligand (L) is achieved by:
A: 1H and 13C-NMR spectra were recorded by using a bruker 300 MHZ (Switzerland).
Chemical Shift of all 1H and 13C-NMR spectra were recorded in (ppm) unit
downfield from internal reference tetramethylsilane (TMS), using D2O as a solvent.
B: Elemental analysis for carbon, hydrogen was using a Euro Vector EA 3000 A Elemental
Analysis (Italy).
C: These analysis (A and B) were done in at AL-al-Bayt University, Al- Mafrag, Jordan.

Synthesis
1. Synthesis of (2-Amino-phenylimino)-acetic acid (L)
To a hot solution of O-phenylenediamine (0.074g. 1m mole) in (5ml) of ethanol, a hot
solution of glyoxylic acid (0.108 g. 1 m mole) in (5ml) of ethanol was added. The solution
was refluxed for 3.5 hrs. Upon cooling a dark brown precipitate formed, was filtered off and
recrystallized from a hot mixture of [(5ml) methanol, (5ml) acetone and (2ml) distilled water].
A dark brown precipitate, yield 85%, melting point 98- 100C, CHN, C= 58.53 (58.51),
H = 4.87 (4.69).
2. Synthesis of complexes
The complex LCoCl.2H2O has been synthesized as follows:
To a hot solution of ligand (L) (0.164g. 1m mole) in (5ml) of ethanol, a hot solution of
cobalt(II) Chloride. hexa hydrate (0.238g. 1m mole) in (5 ml) of ethanol was added. The
precipitate immediately formed, the mixture was boiled and stirring for 10-15 min., filtered
off. Recrestallized from a hot of (10ml) methanol, a dark green precipitate, yield 80%,
decomposed at 110 D.
The physical properties for synthesized ligand (L) and its complexes are shown in
Table (1).
A similar method was used to prepare other complexes: LNiCl.2H2O, L(0.164g 1m
mole), NiCl2.6H2O (0.238g, 1m mole), (10ml) ethanol, (10ml) methanol, yield 90%
decomposed at 200 D, LCuCl.2H2O, L(0.164g, lm mole), CuCl2.2H2O (0.170g, 1m mole),
(10ml) ethanol, (10ml) methanol, yield 82% decomposed at 180 D, LCdCl.2H2O, L(0.164g,
lm mole), CdCl2 .H2O (0.202g, 1m mole), (10ml) ethanol, (10ml) methanol, yield 95%
decomposed at 160 D, LHgCl.2H2O, L(0.164g, lm mole), HgCl2 (0.271g, 1m mole), (10ml)
ethanol, (10ml) methanol, yield 78% decomposed at 190 D, LPb(NO3) 2.2H2O, L(0.164g, lm
mole), Pb(NO3)2 (0.331g, 1m mole), (10ml) ethanol, (10ml) methanol yield 82% decomposed
at 210 D.

IR spectrum of the ligand (L)

The IR spectrum of the (L) Fig. (1) shows new strong bands at (1737, 1668) cm1 are
due to (C=O) of carboxylic group and HC=N imine[8-9] compared with the precursors Figs.
(23), Table (4), which indicate the ligand (L) has been obtained.
Bands corresponding to CH aromatic stretching at (3061) cm1[1,5], NH 2 at (3385,
3363) cm1 are observed[1,3].
Absorption occurs as a sharp peak in the 3466 cm1 is attributed to free (unassociated)
hydroxylCH2 COOH group[5,7,9].

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UV- spectrum of the ligand (L)

The UV- spectrum of (L) Fig. (4), Table (5) was recorded in distilled water with the
range (210 400) nm. The molar absorption at (261) nm may be assigned to an *
transition[10].

NMR spectrum for the ligand (L)

1

H- NMR spectrum of the ligand (L) in DMSOd6 Table (2), Fig. (5) is characterized
by the appearance of chemical shift related to the NH2 protons- aromatic NH2 at 5.10 ppm.,
Chemical shift of aromatic protons showed at 6.777.539 ppm. The characteristic signals at
8.21 ppm. is assigned to HC=N. The COOH signal is found at 10.354 ppm.
13
CNMR of the free ligand Table (3), Fig. (6) shows the HC=N peak at 143.50 ppm.,
the COOH peak at 170 ppm. and carbon peaks for aromatic are detected at 110-125
ppm.[5,11,12].

The IR spectra for the complexes

The free ligand exhibits a strong absorption band at (1737) cm1 due to the stretching
vibration of (C=O) of the carboxylic group. This band is disappeared in the spectra of its
complexes accompanied by the appearance of two bands one in the (1569-1514)cm1 range
due to asymm. (COO) and another bands in the (1398-1375) cm-1 range assigned to symm.
(COO), = (171-139) cm-1 . Fig. (7), Table (4). This indicates that the carboxylic group is
monodentate coordinate[13-14].
The appearance of stretching modes assigned to NH2 and HC=N of C=NH groups
was observed at (33753456) cm-1 and (16601620) cm-1 respectively in free ligand[1-3].
The stretching vibration of azomethine group of the ligand was shifted to lower
frequencies in all spectra, whereas stretching vibrations of NH2 getting broad indicating
additional coordination of metal ions to NH2 and (C=N) group[1-5].
Bands related to coordinate water were observed in all spectra; Cd+2 (704) cm-1, Ni+2
(713) cm-1, Hg+2 (621) cm-1 , Cu+2 (669) cm-1, Co+2 (775) cm-1 and Pb+2 (806) cm-1. Additional
bands were observed at lower frequencies (600400) cm-1 and were attributed to MN, MO
stretching modes[1-2,5,8].
Lead complex shows band at 1660 cm1 due to the NO 3 group.

The electronic absorption spectral and magnetic studies

The Co(II) complex exhibited band around (490) nm (20408) cm-1 (max=300 molar1
cm1) Table (5), which was assigned to 4T1g(F) 4T1 g(P), for high spin octahedral geometry.
The magnetic susceptibility measurements (4.50) BM Table (1), for the solid Co(II)
complex is indicated of three unpaired electrons per Co(II) ion consistent with its odctahedral
environment[9,16-17].
The electronic absorption spectrum of the Ni(II) complex showed broad band center at
(460)nm (21739cm1) (max=400molar1 cm1) assigned to the spin-allowed transition
3
A2g(F)3T1g(P) consistent with octahedral configuration[19,22]. The magnetic moment (2.90) BM
suggested two unpaired electrons per Ni(II) also consistent with octahedral geometry. The electronic
absorption spectrum of Cu(II) complex Fig. (8) showed broad band at (800) nm (12500) cm1
(max=224 molar1 cm1), which was assigned to 2Eg2T2g transition, typical for an octahedral

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configuration. The magnetic moment (1.80) BM suggested one unpaired electron for Cu(II)
consistent with its octahedral environment[18-19].
The spectra of Cd+2, Pb+2 and Hg+2 complexes exhibited charge transfer bands, which
were assigned to a ligand to metal charge transfer[12,20].

Solutions chemistry
Molar ratio
The complexes of the ligand (L) with selected ions (Co+2, Cd+2) were studied in
solution using water as solvents, in order to determine (M:L) ratio in the prepared complexes,
following molar ratio method[21].
A series of solutions were prepared having a constant concentration (C) 103 M of the
hydrated metal salts and the ligand (L). The (M:L) ratio was determined from the relationship
between the absorption of the observed light and mole ratio (M:L) found to be (1:1). The
result of complexes formation in solution are shown in Table (69), Fig. (910).
To determined G[15]:
k = ML/[M][L]
(1)
= (Am As)/ Am
(2)
k = The equation (1) is written to mole ratio (1:1) as the following
(3)
kf = (1 )/ 2 C
= max.b.c.
(4)
kf = stability constant
= decomposition Degree
M = metal ion
L = The ligand
[ ] = concentration
As = The absorption of the equivalent point of mole ratio
Am = The maximum absorption of the mole ratio
C = The complex concentration (mole. L1).
G = - 2.303 RT Log K.
R = 8.303
T = 273 + 25 = 298
Molar conductivity for the complexes of the ligand (L)
The molar conductance of the complexes in water Table (10) lies in the (3.40 0.61) S.
cm2 molar1 range, indicating their non electrolyte nature, except for the Cu complex which
its molar conductance lies in the (119) S. cm2 molar1 range, indicating its electrolytic nature
with (1:1) ratio[22].

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Conclusion
The Schiff base ligand (L) is prepared and charcterised by C, H, N and 1H, 13CNMR.
The ligand (L) is behaved as tridentate mode: NH2, CH=N and O forming octahedral
below:
complexes with M+2, where M+2 = Co, Ni, Cu, Cd, Hg and Pb SchemeCO
O

H2N

OH

OH
NH2

H
H2N

NH2

+ HX

M
H2O

H2O

X2

C
O

M = Co+2, Ni+2, Cu+2, Cd+2, Hg+2 and Pb+2

X = Cl in all complexes except in lead complex
X = ONO2

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1.

2.

3.

4.

5.

6.

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8.

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Table (1): The physical properties for synthesized lignad (L) and its complexes
Empirical
formula

M.P. C

Colour

85

98-100C

Dark brown

LCoCl.2H2O

80

110 D

Dark green

4.50

LNiCl.2H2O

90

200 D

Brown

2.90

LCuCl.2H2O

82

180 D

Dark brown

1.80

LCdCl.2H2O

95

160 D

brown

LHgCl.2H2O

78

190 D

pale brown

LPbNO3.2H2O

82

210 D

brown

L=C8H8O2N2,

NH2
5.10 ppm.

DMF = dimethyl formamide,

Found
(Calc.) %
metal
-

effect

Yield %

Solubility
Watar, methanol,
ethanol, ether, DMF,
DMSO
Watar, methanol,
ethanol, DMF, DMSO
=

(20.00)
19.66
(20.00)
19.31
(21.07)
21.80
(32.18)
32.45
(45.93)
45.46
(44.13)
44.50

=
=
=
=

DMSO = dimethyl sulfoxide,

D = Decomposition

Table (2): 1H-NMR Chemical shifts for L (ppm in D2O)

Aromatic proton
HC=N
COOH
6.77-7.539
8.221 ppm
10.354 ppm

Table (3): 13C-NMR Chemical shifts for L (ppm in D2O)

HC=N
COOH
Aromatic carbons
143.50 ppm.
170 ppm
110-125 ppm.
Table (4): Infrared spectral data (wave number ) cm1 for the ligand (L), precursors
and its complexes
Compound
Glyoxylic acid
O-phenylene
diamine
L

(OH)

(C-H)
Aromatic
3057

assm.
COO
-

1668

3061

1640
1624
1660
1614
1653
1622
1640
1620
1650
1620
1650
1630

3080

1558
1516
1560
1520
1565
1825
1550
1514
1541
1516
1569
1520

1398
1380
1396
1380
1394
1385
1386
1375
1398
1375
1384
1375

170
136
164
140
171
140
164
139
143
141
185
145

775

594
468
572
430
549
457
599
424
580
420
580
450

(C=O) (NH2) (C=N)

3361
-

1745
-

3466

1737

LCoCl.2H2O

LNiCl.2H2O

LCuCl.2H2O

LCdCl.2H2O

LHgCl.2H2O

LPbNO3.2H2O

3387
3363
3385
3363
3408
3375
3404
3375
3448
3376
3456
3379
3450
3380
3450
3376

3060
3134
3080
3064
3065

Chemistry - 270

symm. cm1 Coordinate

water
COO
-

713
669
704
621
806

MN
MO
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Table (5): Electronic spectral data of the ligand (L) and its
wave number (max molar1
Compound
nm
cm1
cm1)
L
261
38314
325
LCoCl.2H2O
490
20408
300
LNiCl.2H2O
460
21739
400
LCuCl.2H2O
800
12500
224
LCdCl.2H2O
267
37453
463
LHgCl.2H2O
268
37313
398
LPbNO3.2H2O
268
37313
398
Where L=C8H8O2N2,
C.T.= Charge Transfer

VM
1 ml
1
1
1
1
1
1
1
1
1

25

metal complexes
Assignments
*
4
T1g(F)4T1 g(P)
4
A2 g(F)4T1g(P)
2
Eg2T2g
C. T.
C. T.
C. T.

Table (6): VM, VL and Absorption of ligand (L),

VM = volume of metal in ml, VL= volume of ligand in ml
[LCoCl.2H2O]
[LCdCl.2H2O]
VL
Abs
VM
VL
0.25
0.772
1 ml
0.25
0.50
1.251
1
0.50
0.75
1.624
1
0.75
1.00
1.950
1
1.00
1.25
2.050
1
1.25
1.50
2.174
1
1.50
1.75
2.289
1
1.75
2.00
2.404
1
2.00
2.25
2.500
1
2.25
2.50
2.601
1
2.50

Proposed
structure
Octahedral
=
=
=
=
=

Abs
0.783
1.092
1.455
1.755
1.964
2.084
2.250
2.403
2.558
2.695

Table (7): The absorbance values against mole ratio values of complex [LCoCl.2H2O]
in solution (1103 mole. L 1) in water at (272.8) nm
No.
L: M
absorbance
1
0.5:1
1.251
2
1:1
1.950
3
2:1
2.404
Table (8): The absorbance values against mole- ratio values of complex [LCdCl.2H2O]
in solution (1103 mole. L 1) in water at 272.8 nm
No.
L: M
absorbance
1
0.5:1
1.092
2
1:1
1.775
3
2:1
2.403
Table (9): Stability constant and G for the ligand (L) complexes
Compounds
As
Am
K
Log K

G
9
[LCoCl.2H2O]
1.950
2.404
0.19
2210
10.43
58.9
[LCdCl.2H2O]
1.755
2.403
0.27
1104
4
22.7
[LCoCl.2H2O] > [LCdCl.2H2O]
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Table (10): The molar conductance of the complexes*

Compound fragment ions
m S.cm2 molar1
LCoCl.2H2O
1.71
LNiCl.2H2O
0.61
LCuCl.2H2O
119
LCdCl.2H2O
1.5
LHgCl.2H2O
3.40
LPbNO3.2H2O
0.71
* Recorded in (water) solvent, where L=C8H8O2N2

Fig. (1): The IR spectrum of the ligand (L)

Fig. (2): The IR spectrum of glyoxylic acid

Fig. (3): The IR spectrum of O-phenylene diamine

Chemistry - 272

ratio
Neutral
Neutral
1:1
Neutral
Neutral
Neutral

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Fig. (4): Electronic spectrum of the ligand (L)

Fig. (5): The 1H-NMR spectrum of the ligand (L)

Fig. (6): The 13C-NMR spectrum of the ligand (L)

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Fig. (7): The IR spectrum of the (NiCl.2H2O) complex

Fig. (8): Electronic spectrum of the (CuCl.2H2O) complex

3.0

2.5

2.0

Absorbtion

1.5

1.0

0.5

0.0
0.0

0.5

1.0

1.5

2.0

2.5

Mole Ratio

Fig. (9): The mole ratio curve of complex [CoCl.2H2O] in solution (110-3 mole.
l-1) at (=272.8 nm)
3.0

2.0

Absorbtion

No.

1.0

0.0
0.0

0.5

1.0

1.5

2.0

2.5

Mole Ratio

Fig. (10): The mole ratio curve of complex [CdCl.2H2O] in solution (110-3 mole.
l-1) at (=272.8 nm)

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- 2) - ( - )(L
-

1H, 13CNMR ).(C.H.N

) (L
.
.
: -
.

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